JPH05286774A - Production of heat resistant fiber-reinforced composite material - Google Patents

Abstract

PURPOSE:To easily obtain the high-performance heat resistant fiber-reinforced composite material having a graded compsn. by packing a matrix by a vapor deposition method simultaneously while changing the compsn. during taking up of a continuous fibers at the time of producing the composite material by a winding method. CONSTITUTION:A raw material continuous fiber bobbin 3 is rotatably disposed in a chamber 10 having a vent hole 1 and a gaseous raw material injection hole 2. The continuous fiber 5 (e.g.; carbon fiber) is supplied from the raw material continuous fiber bobbin 3 to a traverser 7 and after the feed position is controlled, the continuos fiber 5 is wound to form a filament winding molding 9. While the molding is formed, the gaseous raw material 8 is supplied via a flexible tube 4 and a nozzle 6 from the gaseous raw material injection hole 2 into the chamber and the matrix is packed by the vapor deposition method. The heat resistant fiber-reinforced composite material having the desired graded compsn. is produced by changing the compsn. of the matrix to be packed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat resistant fiber reinforced composite material and a method for producing the same, and more particularly to a three-dimensional heat resistant fiber reinforced composite material required to have heat resistance and high temperature strength and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, rocket nozzles, leading edges, gas turbine engine parts, and the like have been required to have three-dimensional parts and materials which are required to have heat resistance and high temperature strength. As such a material, a fiber-reinforced composite material such as a C / C composite has been conventionally used.

However, in the case of producing a three-dimensional shape from a fiber-reinforced composite material, it is necessary to use long fibers in order to improve the performance, and the orientation of the fibers is also a problem. Therefore, conventionally, the filament winding method (hereinafter referred to as F / W method) or the three-dimensional weaving is used,
A method of filling a matrix after manufacturing a near shape (having a close shape) of a fiber substrate having a desired three-dimensional shape is used.

[0004]

As described above, in order to improve the performance of the fiber-reinforced composite material, the F / F has hitherto been improved.
The W method or the like was used.

However, in the conventional method for manufacturing a fiber-reinforced composite material, since a near shape of a fiber base material having a desired three-dimensional shape is manufactured and then a matrix is filled to densify the material, a particularly thick material or a complicated shape is formed. However, it was difficult to arbitrarily control the composition of the material, such as the difficulty of increasing the internal density. Here, for example, in the case of a C / ceramics heat-resistant and oxidation-resistant panel or the like, a dense material having a high ceramic content is desired on the side exposed to high temperature air, and a carbon fiber is contained to some extent to improve strength on the opposite side. A higher amount of material is desired. In order for such a material to sufficiently exhibit its performance, it is necessary that the material composition (chemical composition of matrix, matrix content, fiber content, porosity) continuously changes between both surfaces described above. However, conventionally, it was difficult to arbitrarily control the composition in the material as described above, and thus it was also difficult to continuously change the material composition. in this way,
Heretofore, it has been difficult to manufacture a high-performance heat-resistant fiber-reinforced composite material having a gradient in material composition.

The present invention has been made to solve the above problems, and provides a high-performance heat-resistant fiber-reinforced composite material having an arbitrary composition in an arbitrary portion of the material and a method for producing the same. With the goal.

[0007]

The method for producing a heat-resistant fiber-reinforced composite material according to claim 1, wherein the heat-resistant fiber-reinforced composite material is produced by a filament winding method using continuous fibers. Method,
During the winding of the continuous fibers, a step of simultaneously filling the matrix by a vapor deposition method and changing the composition of the filled matrix is provided.

In the heat resistant fiber reinforced composite material according to the second aspect, the composition of the matrix continuously changes in at least a part of the material.

[0009]

In the method of manufacturing the heat resistant fiber reinforced composite material according to the first aspect, the matrix is filled by the vapor deposition method at the same time while the continuous fiber is wound, and the composition of the filled matrix is changed. A heat resistant fiber reinforced composite material having an arbitrary composition (for example, a continuous gradient composition) at an arbitrary portion therein can be easily manufactured.

In the heat-resistant fiber-reinforced composite material according to claim 2, since the composition of the matrix continuously changes at least in a part of the material, for example, the side exposed to the high temperature atmosphere and the high temperature atmosphere are exposed. When there is both surfaces on the non-exposed side, it is possible to provide a heat resistant fiber reinforced composite material having a gradient composition that is most suitable for the use conditions.

[0011]

First, the essence of the present invention will be described as a premise for explaining the embodiments.

According to the present invention, when a heat-resistant fiber-reinforced composite material is produced by the F / W method using continuous fibers, the CVD method (chemical vapor deposition method) or the PVD method (physical vapor deposition method) are simultaneously applied during winding. ) And the like are used to fill the matrix, and the composition of the matrix (and the amount of precipitation of the matrix) is changed depending on the position of the molded body. Thus, a heat resistant fiber reinforced composite material having a predetermined shape is produced. That is, during the winding of the F / W method, the portion immediately after the continuous filaments of the molded intermediate are wound up by the CVD method or the P method.
The matrix is sequentially packed by the VD method to densify.
Specifically, the matrix raw material gas is blown using a nozzle or the like only to the portion immediately after the continuous fiber is wound up on the molding intermediate to generate and fill the matrix. At this time, the amount of matrix deposition and the matrix composition are changed by changing the composition ratio flow rate of the matrix source gas, the addition amount of the carrier gas, and the winding speed. The composition of the matrix source gas is determined by changing the ratio of the constituents and the number of constituents of the constituent matrix. This allows for any composition (matrix composition, matrix content,
A heat-resistant fiber-reinforced composite material having a carbon fiber content and a porosity) and having a continuous gradient composition at an arbitrary ratio with the periphery can be produced.

At this time, the continuous fibers used are heat-resistant.
Of carbon fiber and cement
Ramix fiber (SiC, Si₃N_Four, ZrO₂, Al
₂O ₃Etc.), metal fibers (tungsten etc.), boron fibers
Of these, those containing at least one type are preferred
Yes. Also, as a matrix, heat resistance and high temperature strength
It is an excellent substance, carbon, boron, ceramics.
(SiC, Si₃N_Four, TiC, ZrC, ZrO₂, H
fC, HfO₂, HfSi₂, HfSiO₂, Al₂O
₃Etc.) that includes at least one type is preferred
Yes.

Depending on the precursor of the matrix raw material, CV
Select whether to use the D method or the PVD method. fiber/
The matrix ratio, the orientation state of the matrix, the porosity, etc. are selected according to the usage conditions. That is, F / W
It is necessary to optimize the winding speed, nozzle shape, CVD or PVD conditions, etc.

Based on the essence of the present invention described above, the following materials were actually produced. That is, using the F / W method, a molded body having an outer diameter of 6 cm, an inner diameter of 2 cm and a height of about 7 cm was produced by the manufacturing method described below. (Example 1) (1) First, an apparatus used in this example will be described. FIG. 1 is a schematic configuration diagram showing an apparatus for performing the method for manufacturing a heat resistant fiber reinforced composite material (F / W method + CVD method) of the present invention. With reference to FIG. 1, this apparatus includes a chamber 10, an exhaust hole 1 provided at a predetermined position of the chamber 10, and a source gas injection for injecting a source gas provided at a predetermined position of the chamber 10. Hole 2 and chamber 10
Raw material continuous fiber bobbin 3 rotatably mounted at a predetermined position in the inside, traverser 7 for controlling the feeding position of continuous fiber 5 supplied from raw material continuous fiber bobbin 3, and continuous fiber 5 sent from traverser 7. F / W molded body 9 formed by winding the material, a nozzle 6 for supplying the raw material gas 8 to the F / W molded body 9 while forming the F / W molded body 9, and a raw material gas injection port 2 and a flexible tube 4 for supplying a raw material gas to the nozzle 6.
Using such a device, in Example 1, the CV was used in the device.
While carrying out D, a C / C composite molded body was produced by the F / W method. The heating was performed by energizing graphite, which is the core material of the F / W molded body 9. The temperature is 1100
C., methane and silicon tetrachloride were used as the source gas, and hydrogen was used as the carrier gas. The material composition (carbon / silicon carbide ratio in the matrix) of the inner layer portion and outer layer portion of the cylinder was continuously changed by changing the composition of these three gases and the spraying amount. The pressure inside the apparatus was 50 Torr. (Example 2) While performing CVD in the apparatus shown in FIG. 1, a C / C composite molded body was produced by the F / W method. The heating was performed by energizing graphite (not shown) of the core material. The temperature was 1300 ° C., methane and silicon tetrachloride were used as the source gas, and hydrogen was used as the carrier gas. By changing the composition of these three kinds of gas and the spraying amount, the material composition of the cylinder inner layer part and the outer layer part (carbon fiber /
Matrix ratio, carbon / silicon carbide ratio in the matrix)
Was continuously changed. The pressure in the device is about 50 Torr
Met. Example 3 A C / C composite molded body was produced by the F / W method while performing CVD in the apparatus shown in FIG. The heating was performed by energizing graphite (not shown) of the core material. The temperature was 1300 ° C., methane and silicon tetrachloride were used as the source gas, and hydrogen was used as the carrier gas. The material composition (carbon fiber / matrix ratio, carbon / silicon carbide ratio in the matrix, and porosity) of the inner and outer layers of the cylinder is continuously changed by changing the composition of these three gases and the spray amount. Let The pressure inside the device is 50To
It was rr.

The following physical properties were evaluated for each of Examples 1 to 3 described above. (1) Measurement A measurement sample was cut out from each of the materials obtained in Examples 1 to 3, and the apparent density and the porosity were measured. FIG. 2 is a cross-sectional view for explaining the sampling position of the physical property measurement sample from the trial-produced sample material. Referring to FIG. 2, along the radial direction of the sample cross section 104, the inner layer 103,
The intermediate layer 102 and the outer layer 101 are cut off and cut out as a measurement sample.

Shape of sample: length × width × height = 4 mm × 4 m
m × 4 mm Number: n = 5 (for each part) (2) Test results The carbon fiber volume content and the matrix volume content were calculated from the porosity and apparent density obtained by the above measurement. The results are shown in Table 1 below.

[0018]

[Table 1]

Referring to Table 1 above, the material obtained in Example 1 has a gradient composition in which the porosity is small and the matrix continuously changes from silicon carbide to carbon from the outer layer portion to the inner layer portion. was gotten. Further, when the surface composition of the matrix composition was analyzed by an analytical SEM, it was observed that the silicon carbide content continuously changed.

The material obtained in Example 2 has a low porosity, the matrix continuously changes from silicon carbide to carbon from the outer layer portion to the inner layer portion, and the carbon fiber content also continuously changes. A product having a gradient composition was obtained. As a result of surface analysis of the matrix composition by analytical SEM, it was observed that the silicon carbide content continuously changed. When the structure was observed with a polarization microscope, it was observed that the carbon fiber content continuously changed.

In the material obtained in Example 3, the matrix continuously changed from silicon carbide to carbon from the outer layer portion to the inner layer portion, the carbon fiber content also continuously changed, and the porosity was maximum in the middle layer portion. Those having a graded composition that takes a value were obtained. When the surface composition of the matrix composition was analyzed by analytical SEM, it was observed that the silicon carbide content continuously changed. When the structure was observed with a polarization microscope, it was observed that the carbon fiber content continuously changed and the porosity continuously changed.

[0022]

According to the first aspect of the present invention, while the continuous fiber is being wound, the matrix is filled by the vapor deposition method at the same time and the composition of the filled matrix is changed, so that an arbitrary portion in the material can be obtained. It is possible to easily produce a high-performance heat-resistant fiber-reinforced composite material having an arbitrary matrix composition in an arbitrary range of 1 and having a continuous gradient composition in an arbitrary ratio with the surroundings. In addition to the matrix composition, if the precipitation amount of the matrix is changed, any matrix composition, matrix content,
A heat resistant fiber reinforced composite material having a carbon fiber content and a porosity can be manufactured.

According to the second aspect of the present invention, the composition of the matrix is continuously changed in at least a part of the material so that, for example, the side exposed to the high temperature atmosphere and the side not exposed to the high temperature atmosphere are exposed. It is possible to provide the heat-resistant fiber-reinforced composite material having the best performance depending on the usage situation such as having both surfaces.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an apparatus used in a method for producing a heat resistant fiber reinforced composite material of the present invention.

FIG. 2 is a cross-sectional view for explaining a sampling position of a physical property measurement sample from a prototype sample material.

[Explanation of symbols]

 1: Exhaust hole 2: Raw material gas injection hole 3: Raw material continuous fiber bobbin 4: Flexible tube 5: Continuous fiber 6: Nozzle 7: Traverser 8: Raw material gas 9: F / W compact 10: Chamber 101: Outer layer 102: Intermediate Layer 103: Inner layer 104: Sample cross section

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takatoshi Takemoto 1-1-1 Kunyokita, Itami City, Hyogo Prefecture Sumitomo Electric Industries Itami Works

Claims (2)

[Claims] 1. A method for producing a heat-resistant fiber-reinforced composite material, which comprises producing a heat-resistant fiber-reinforced composite material by a filament winding method using continuous fibers, wherein a matrix is formed by vapor deposition simultaneously with winding the continuous fiber. The method for producing a heat-resistant fiber-reinforced composite material, comprising the steps of: 2. A heat resistant fiber reinforced composite material, wherein the composition of the matrix is continuously changing in at least a part of the material.